Closed loop carbon monoxide self-contained nickel carbonyl deposition process

ABSTRACT

A closed loop, carbon monoxide self-contained preferably continuous process and apparatus for the production of nickel or nickel coated objects by nickel vapor deposition (NVD), comprising placing an object to be treated with nickel carbonyl in a deposition chamber; feeding a gaseous mixture of nickel carbonyl and carbon monoxide to the chamber; producing the nickel or nickel coated object and a nickel carbonyl-depleted gaseous mixture; removing nickel carbonyl from the nickel carbonyl-depleted gaseous mixture in a primary and subsequent secondary condensation unit and, preferably, a tertiary condensation unit to produce an essentially nickel carbonyl-free gas. The secondary and tertiary condensation units operably freeze out and subsequently thaw nickel carbonyl and most preferably each comprises a pair of units linked in parallel arrangement operative in alternating, alternate freeze-thaw modes. Carbon monoxide-containing gas is recycled to a nickel carbonyl reactor. The process and apparatus provides a more economic to operate, safe and more operably reliable than prior art NVD processes.

FIELD OF THE INVENTION

This invention relates to nickel vapour deposition processes for use inthe manufacture of nickel or nickel coated objects, particularly, toeffluent gas recycling in said processes; and to apparatus for use insaid processes.

BACKGROUND TO THE INVENTION

Chemical vapour deposition is a well-known method for depositing filmsor coatings on substrates. One known chemical vapour used for depositinga nickel film or coating on a substrate is nickel carbonyl in theso-called Nickel Vapour Deposition process (NVD). Typically, thesubstrates to be nickel coated are heated within a reaction ordeposition chamber to a predetermined suitable reaction temperature,typically 110° C.-180° C. in an atmosphere of nickel carbonyl, Ni(CO)₄.The nickel carbonyl reacts at the surface of the heated substrate todeposit the Ni film or coating thereon.

Nickel carbonyl from a liquid supply tank flows through a vapourizerwhere it is converted into a gas stream to which gaseous stream may beadded a small amount of carrier gas, such as carbon monoxide.

Typically, nickel carbonyl vapour is continuously introduced to thedeposition chamber, wherein it reacts to produce elemental nickel andcarbon monoxide by-product. The spent gas is continuously purged fromthe chamber in order to maintain proper circulation of reactive nickelcarbonyl across the surfaces of the substrates. The substrates may beheated according to well-known methods, such as heat conduction,radiation, inductance and the like.

The spent gases which contain nickel carbonyl in excess of 30% W/Wgenerally undergo a nickel carbonyl reclamation process to substantiallyremove the nickel carbonyl before the spent stream enters anincinerator. The incinerator is used to ensure complete thermaldestruction of nickel carbonyl prior to letting the combustion productsinto the environment.

The recovered nickel carbonyl is, typically, passed to a liquid supplytank. Nickel carbonyl is produced in a nickel carbonyl generatorcontaining nickel powder of a suitable morphology in a packed bedthrough which is passed fresh carbon monoxide gas from a storagecylinder to generate fresh nickel carbonyl. The gaseous mixture ispassed through a condenser wherein the nickel carbonyl is condensed andfed to a storage tank. A compressor recirculates the resultant gas backto the nickel carbonyl generator.

The above general process represents a typical operation involving, ineffect two distinctive processes for generating, reacting andre-generating nickel carbonyl with non-recycled carbon monoxide.

The above process, thus suffers from the disadvantages of wasting carbonmonoxide generated as a by-product by the burning thereof in anincinerator and, also, the need to have the incinerator continuouslyoperating in a continuous NVD process. Moreover, nickel oxide isproduced in the incinerator during nickel carbonyl combustion.

U.S. Pat. No. 5,766,683, issued Jun. 16, 1998, to New American TECdescribes a reclaim system for cooling the gases received from theplating system and cooling them to a temperature just above the freezingpoint of nickel carbonyl to condense out and recover the liquidcarbonyl. The reclaim system includes a reclaim condenser and a vaporrecovery gas receiver for receiving vapors from the reclaim system. Thevapor recovery system includes a first stage compressor operativelyconnected to a first stage receiver for pressurizing the vapor to about25 PSIG, and a first stage condenser operatively connected to the firststage compressor for cooling the vapors. A conduit communicates thevapor recovery system to the reactor system for forwarding the cooledvapors to a recycle pump receiver in the reactor system. A furthercompressor is provided in the reactor system for compressing the gasesfrom the recycle pump receiver to about 65 PSIG. This system recoversand recycles substantial amounts of the nickel carbonyl and wherein therequirements for carbon monoxide are substantially reduced. However,U.S. Pat. No. 5,766,683 does not satisfactorily address the fullrecovery of nickel carbonyl for recycle within the system.

There is, therefore, a need for an improved NVD process which is moreeconomic, safe and reliable.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide an improved NVDprocess which is more economic to operate, safe and more operablyreliable than present prior art NVD processes.

It is a further object of the invention to provide a moreenvironmentally acceptable NVD process having a reduced need for use ofa carbon monoxide incinerator during operations.

It is a yet further object of the invention to provide apparatus for usein aforesaid NVD processes.

Accordingly, in one broad aspect the invention provides a closed loop,carbon monoxide self-contained process for the production of nickel or anickel-coated object by the nickel vapour deposition process, comprising

(a) placing an object to be treated with nickel carbonyl by said nickelvapour deposition process in a deposition chamber;

(b) feeding a gaseous mixture comprising nickel carbonyl and carbonmonoxide to said deposition chamber;

(c) depositing nickel on said object to produce said nickel ornickel-coated object in said chamber and a nickel carbonyl-depletedgaseous mixture;

(d) removing said nickel carbonyl-depleted gaseous mixture from saidchamber;

(e) removing nickel carbonyl from said nickel carbonyl-depleted gaseousmixture in a primary nickel carbonyl condensation unit to produce afirst reduced-concentration nickel carbonyl-containing gas; theimprovement comprising

(f) condensing said first reduced-concentration nickelcarbonyl-containing gas in a secondary condensation unit operative in analternate freeze-thaw mode by, stepwise,

(i) freezing said first reduced-concentration nickel carbonyl-containinggas to produce a first solid nickel carbonyl;

(ii) melting said first solid nickel carbonyl to produce a first liquidnickel carbonyl;

(iii) removing said first liquid nickel carbonyl from said secondarycondensation unit to produce a second reduced concentration nickelcarbonyl-containing gas having a nickel carbonyl concentration of lessthan 5 V/V %; and

(g) feeding said second reduced-concentration nickel carbonyl-containinggas to a nickel carbonyl reactor containing nickel powder to produce afresh gaseous mixture comprising fresh nickel carbonyl and carbonmonoxide.

Two process loops, one nickel carbonyl generation and the otherdecomposition are connected via recycled carbon monoxide and liquidcarbonyl transfer links. The two loops can operate independently fromeach other or in tandem as is preferred for reasons outlinedhereinbefore.

The preferred nickel carbonyl reclaim system of use in the inventionprovides for successful operation and integration of the two loops.After the deposition chamber there is a preferred 3-stage carbonylreclamation process. In the first or primary condensation unit nickelcarbonyl is condensed. The secondary reclamation unit comprises a pairof condensation units which essentially reduces the nickel carbonylconcentration to below 1%. The double units, alternatively andsimultaneously, freeze or thaw out nickel carbonyl. The switching fromon unit to the other is accomplished by a suitable nickel carbonylconcentration detection system in the process stream.

Accordingly, the invention provides in a preferred embodiment theprocess as hereinbefore defined, for continuous operation having aplurality of said secondary condensation units linked in parallelarrangement and operative in alternating, alternate freeze-thaw modes.

In the next stage, carbon monoxide-nickel carbonyl gas mixture iscompressed and traces of nickel carbonyl are removed by a 3^(rd) reclaimsystem comprising a pair of condensation units, which reclaims traces ofnickel carbonyl to yield pure carbon monoxide wherein carbon monoxidewas the sole carrier gas. Reclaim 3 system operates on the sameswitching principles as reclaim 2.

Accordingly, in a more preferred embodiment, the invention, ashereinabove defined, further comprising condensing said secondreduced-concentration nickel carbonyl-containing gas in a tertiarycondensation unit operative in an alternate freeze-thaw mode, bystepwise,

(iv) freezing said second reduced-concentration nickelcarbonyl-containing gas to produce a second solid nickel carbonyl;

(v) melting said second solid nickel carbonyl to produce a second liquidnickel carbonyl;

(vi) removing said second liquid nickel carbonyl from said tertiarycondensation unit; to produce a third reduced-concentration nickelcarbonyl-containing gas having a nickel carbonyl concentration of lessthan 500 p.p.m.; and

(h) feeding said third reduced-concentration nickel carbonyl-containinggas to a nickel carbonyl reactor containing nickel powder to produce afurther fresh gaseous mixture comprising nickel carbonyl and carbonmonoxide.

Selection of suitable carbon monoxide diaphragm type compressors is mostpreferred for safe running of the process.

The reactor in the carbonyl generation loop can have a continuous feedof nickel powder. Suitable controlled reactor bed temperature ismaintained via a separate heat management system. Highly toxic reactorresidue is handled by an auxiliary suction system.

Transfer of liquid nickel carbonyl during the process between generationto decomposition loop is accompanied without pumps by pressurizingstorage cylinders.

In a further feature, the invention provides a method of recoveringnickel carbonyl in a nickel deposition system which includes a reactorsystem, a plating system, a reclaim system and a vapor recovery systemcomprising the steps of producing liquid nickel carbonyl, vaporizing theliquid nickel carbonyl and applying the vaporized nickel carbonyl to asubstrate to deposit nickel thereon and to release carbon monoxide,cooling the gases after the deposition of nickel on said substrate to atemperature below the freezing point of nickel carbonyl to condense outnickel carbonyl to a solid; subsequently allowing said solid nickelcarbonyl to melt and recovering liquid nickel carbonyl from said solidnickel carbonyl.

In a further aspect the invention provides an improved nickel depositionapparatus having a nickel carbonyl reactor unit, a nickel depositionunit, a nickel carbonyl vapour recovery system having a primarycondensation unit and a secondary condensation unit the improvementcomprising means for freezing nickel carbonyl to a solid within saidsecondary condensation unit, means for melting said solid nickelcarbonyl to a liquid; means for recovering said liquid nickel carbonyl;and means for recovering nickel carbonyl depleted gaseous mixture.

Preferably, the apparatus has a plurality, preferably, a pair of saidsecondary condensation units linked in parallel and means foroperatively controlling said units in alternating, alternate nickelcarbonyl freeze-thaw modes.

More preferably, the apparatus further comprises a tertiary condensationunit for freezing nickel carbonyl out of said recovered nickelcarbonyl-depleted gaseous mixture to a solid state, means for meltingsaid frozen nickel carbonyl to a liquid and means for recovering saidliquid nickel carbonyl.

Yet more, preferably, the apparatus comprises a pair of said tertiarycondensation units linked in parallel and means for operativelycontrolling said units in alternating, alternate nickel carbonylfreeze-thaw modes.

BRIEF DESCRIPTION OF THE DRAWINGS

In order that the invention may be better understood, a preferredembodiment will now be described by way of example only wherein:

FIG. 1 represents a schematic flow sheet of a process and apparatusaccording to the invention.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

FIG. 1 shows generally as 10, an apparatus and process flow sheetaccording to the invention.

Liquid nickel carbonyl from storage tank 12 is passed at ambienttemperature through conduit line 14 at 40 psi with carbon monoxidecarrier gas prior to entering vaporizer 18. The liquid nickel carbonylflow rate in conduit 14 is measured by a mass flow meter 20, which sendsthe information to a flow control valve 22 whereby the flow iscontrolled and adjusted to the desired value. Carbon monoxide carriergas from carbon monoxide storage tank 16 (84) is mixed from line 24 withthe nickel carbonyl to form a 10% CO W/W 90% Ni(CO)₄.

Vaporizer 18 vaporizes the liquid nickel carbonyl to a temperature ofapproximately 87° C. The vaporized mixture is passed through heatedconduit 26 to deposition chamber 28, wherein the gas is dispersedthrough a manifold 30 to contact a heated mandrel 32, having a substrate34 at a temperature of approximately 180° C. At this temperature, thenickel carbonyl decomposes at the surface of substrate 34 to produce anickel metal coating on substrate 34. The temperature and residence timeof the gaseous mixture in the chamber is such as to effect about a 60%nickel carbonyl decomposition rate. The remaining non-decomposed nickelcarbonyl, CO carrier gas and CO produced from the decomposition exitschamber 28 through heated conduit 36 at about 60° C. to a refrigerationunit 40, wherein most of the nickel carbonyl is liquefied and fedthrough line 42 to storage tank 44. The gas concentration in line 36 ismeasured by a UV gas concentration cell meter (not shown), and,typically, has a nickel carbonyl concentration ranging from 30-80% V/V,temperature of between 82-85° C. and a pressure of about 0.05 bar..

The gaseous mixture exiting unit 40, typically, has a nickel carbonylconcentration of between 6.5-8.0 V/V %, temperature of -15° to -17° C.,pressure of about 0.05 bar, and is passed through conduit 46 and then toone of two refrigerated reclamation units 48 or 50 through lines 52 or54, respectively, as hereinbelow explained.

Units 48, 50 are identical in construction and operation and represent apair of refrigeration units which operate in parallel in distinctfreezing cycles, from either a "freezing of nickel carbonyl" mode or a"thawing of carbonyl" mode as may be selected. The units in their freezemode, typically, provide solid nickel carbonyl at a temperature selectedfrom -55° to -58° C. In operation, when unit 48 is in its freezing mode,i.e. operating at its coldest temperature, exhaust gas from conduit 46is passed through conduit 52 to unit 48, wherein the vast majority ofthe nickel carbonyl in the gas is frozen. Small amounts of nickelcarbonyl gas pass through unit 48 until either the back-pressure in thesystem exceeds a pre-determined value, or if the nickel carbonyl gaslevel passing through line 60 exiting unit 48 exceeds a pre-determinedlevel as measured by UV analyzer 62. Typically, the gaseous mixture inline 60 has a nickel carbonyl concentration less than 5 V/V %, andgenerally of between 0.35-0.55 V/V % and a temperature of between 15° to20° C. at a pressure of about 30 bar after compression as hereinbelowdescribed.

When either of the above two conditions is met, other unit 50 isswitched to the freezing mode and the exhaust gas flow is switched tounit 50. First unit 48 is then switched over to the "thaw" mode whichmeans that the unit freezing system is switched off and the unit heaters(not shown) are turned on. The thaw mode melts the frozen nickelcarbonyl into a liquid form, which is gravity drained to storage tank 44via line 56. The above procedure in respect of unit 50 occurs when unit50 reaches its critical condition whereby the thaw/freeze processswitches back to the original thaw setting with liquid nickel carbonyldropping through conduits 64 and 56 into storage tank 44.

Thus, further nickel carbonyl-depleted exhaust gas leaves units 48 and50 through lines 60, 66, respectively, to pass through common line 68 toa diaphragm compressor 70 to provide a compressed gas mixture. Thecompressed gas passes subsequently through an additional or thirdreclaiming system consisting of dual refrigeration units 72, 74analogous to units 48, 50 and related analogous conduits so designed asto be identical in operation to reclaim system 2 with the exception thatreclaim system 3 operates at a higher pressure. Thus, units 72,74 areidentical in constructions and operation and represent a pair ofrefrigeration units which also operate in parallel in distinct freezingcycles, from either a "freezing of nickel carbonyl" mode or a "thawingof carbonyl" mode as may be selected. In operation, when unit 72 is inits freezing mode, i.e. operating at its coldest temperature, compressor70 exhaust gas from conduit 76 is passed through conduit 78 to unit 72,wherein the vast majority of the nickel carbonyl in the gas is frozenout. Essentially, nickel carbonyl-free gas passes out of unit 72 untilthe back-pressure in the system exceeds a pre-determined value.Typically, the nickel carbonyl is at a concentration of less than 500p.p.m. and, generally, between 100-200 p.p.m., at a gaseous mixturetemperature of about -50° C. and pressure of 30 bar.

When the above condition is met, refrigeration unit 74 is switched toits freezing mode and conduit 76 exhaust gas flow is switched to unit74. First unit 72 is then switched over to its "thaw" mode, which meansthat its unit freezing system is switched off and its unit heaters (notshown) are turned on. In a thaw mode, the frozen nickel carbonyl meltsinto a liquid, which is then transferred to storage tank (80) via line82. The above procedure in respect of unit 74 is conducted until unit 74reaches its critical condition whereby the thaw/freeze process isswitched back to its original thaw setting, with the resultant liquidnickel carbonyl being subsequently transferred through conduit 82 intostorage tank 80.

Thus, further essentially nickel carbonyl-free compressed exhaust gasleaves units 72 and 74 through lines 84, 85, respectively, to pass tocarbon monoxide storage tank 16. Tank 16 is also a reservoir for acarbon monoxide supply to nickel carbonyl producer reactor 86 containinga bed of nickel powder raw material. Reactor 86 receives carbon monoxidefrom tank 16 through line 88 and operates at a temperature selected from70°-115° C. The addition of CO through line 88 provides for theproduction of nickel carbonyl, wherein the flowthrough of CO depends onthe reactivity of the nickel powder, i.e. the greater the productionrate, the more CO that is consumed.

Regenerated nickel carbonyl/CO mixture exits reactor 86 through line 90to nickel carbonyl liquid condenser 92 operating at a temperature ofbetween -18° and 0° C., wherein liquid nickel carbonyl is condensed andgravity fed through conduit 94 to storage tank 96. The resultant gasmixture exits condenser 92 through line 98 to generator recirculatingcompressor 100, which recycles the gas back to reactor 86 for nickelcarbonyl production until the nickel powder is fully converted to nickelcarbonyl.

Liquid nickel carbonyl is subsequently transferred from storage tank 96through conduit 102 to storage tanks 44 and 12, as required.

Thus, it can be seen that the embodiment hereinabove described providesfor a fully closed carbon monoxide recycle system wherein initial carbonmonoxide is used as a carrier gas, converted to nickel carbonyl andsubsequently re-generated from the nickel carbonyl. The only materialadded and subsequently removed from the system is metallic nickel, whichis added as powder and removed as an object or coating as nickel plate,foil and the like. Judicious selection of reactor temperatures,decomposition chamber temperatures and conduit temperatures enablesproper utilization of the chemical reactants. Suitable gas pressures andflow rates are readily attained and controllable.

Use of a second stage double, in parallel, refrigeration unit systemenables continuous operation of the process. Further, use of a thirdstage double, in parallel, refrigeration unit system further providesenhanced nickel carbonyl recovery values for recycle within the carbonmonoxide fully closed system.

Although this disclosure has described and illustrated preferredembodiments of the invention, it is to be understood that the inventionis not restricted to those particular embodiments. Rather, the inventionincludes all embodiments which are functional or mechanical equivalenceof the specific embodiments and features that have been described andillustrated.

We claim:
 1. An improved closed loop, carbon monoxide self-containedprocess for the production of nickel or a nickel-coated object by thenickel vapor deposition process, comprising(a) placing an object to betreated with nickel carbonyl by said nickel vapor deposition process ina deposition chamber; (b) feeding a gaseous mixture comprising nickelcarbonyl and carbon monoxide to said deposition chamber; (c) depositingnickel on said object to produce said nickel or nickel-coated object insaid chamber and a nickel carbonyl-depleted gaseous mixture; (d)removing said nickel carbonyl-depleted gaseous mixture from saidchamber; (e) removing nickel carbonyl from said nickel carbonyl-depletedgaseous mixture in a primary nickel carbonyl condensation unit toproduce a first reduced-concentration nickel carbonyl-containing gas;the improvement comprising (f) condensing said firstreduced-concentration nickel carbonyl-containing gas in a secondarycondensation unit operative in an alternate freeze-thaw mode by,stepwise,(i) freezing said first reduced-concentration nickelcarbonyl-containing gas to produce a first solid nickel carbonyl; (ii)melting said first solid nickel carbonyl to produce a first liquidnickel carbonyl; (iii) removing said first liquid nickel carbonyl fromsaid secondary condensation unit; to produce a second reducedconcentration nickel carbonyl-containing gas having a nickel carbonylconcentration of less than 5 V/V %; and (g) feeding said secondreduced-concentration nickel carbonyl-containing gas to a nickelcarbonyl reactor containing nickel powder to produce a fresh gaseousmixture comprising fresh nickel carbonyl and carbon monoxide.
 2. Aprocess as defined in claim 1 for continuous operation comprising aplurality of said secondary condensation units linked in parallelarrangement and operating in alternate freeze-thaw modes.
 3. A processas defined in claim 1 further comprising condensing said secondreduced-concentration nickel carbonyl-containing gas in a tertiarycondensation unit operative in an alternate freeze-thaw mode, bystepwise,(iv) freezing said second reduced-concentration nickelcarbonyl-containing gas to produce a second solid nickel carbonyl; (v)melting said second solid nickel carbonyl to produce a second liquidnickel carbonyl; (vi) removing said second liquid nickel carbonyl fromsaid tertiary condensation unit; to produce a thirdreduced-concentration nickel carbonyl-containing gas having a nickelcarbonyl concentration of less than 500 p.p.m.; and (h) feeding saidthird reduced-concentration nickel carbonyl-containing gas to a nickelcarbonyl reactor containing nickel powder to produce a further freshgaseous mixture comprising nickel carbonyl and carbon monoxide.
 4. Aprocess as defined in claim 3 wherein said third reduced-concentrationnickel carbonyl-containing gas has a nickel-carbonyl concentration ofless than 200 p.p.m.
 5. A process as defined in claim 3 furthercomprising condensing said second reduced-concentration nickelcarbonyl-containing gas in said tertiary condensation unit at a pressuregreater than 25 bar.
 6. A process as defined in claim 3 furthercomprising recycling said nickel carbonyl obtained from any of steps(e), (iii), (vi), (g) and (h) to said deposition chamber.
 7. A processas defined in claim 1 further comprising condensing said firstreduced-concentration nickel carbonyl-containing gas in said secondarycondensation unit at a pressure greater than 0.03 bar.
 8. A method ofrecovering nickel carbonyl in a nickel deposition system which includesa reactor system, a plating system, a reclaim system and a vaporrecovery system comprising the steps of producing liquid nickelcarbonyl, vaporizing the liquid nickel carbonyl and applying thevaporized nickel carbonyl to a substrate to deposit nickel thereon andto release carbon monoxide, cooling gases after the deposition of nickelon said substrate to a temperature below the freezing point of nickelcarbonyl to condense out nickel carbonyl to a solid; subsequentlyallowing said solid nickel carbonyl to melt and recovering liquid nickelcarbonyl from said solid nickel carbonyl.